CN109293928B - Composite flocculant for treating papermaking wastewater and preparation method thereof - Google Patents
Composite flocculant for treating papermaking wastewater and preparation method thereof Download PDFInfo
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- CN109293928B CN109293928B CN201810963486.7A CN201810963486A CN109293928B CN 109293928 B CN109293928 B CN 109293928B CN 201810963486 A CN201810963486 A CN 201810963486A CN 109293928 B CN109293928 B CN 109293928B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
Abstract
The invention provides a preparation method of a composite flocculant for treating papermaking wastewater, which comprises the following steps: the preparation method comprises the steps of I preparing a triazine polyamide polycondensate, II preparing a triazine polyamide acrylonitrile copolymer, III modifying active silicic acid, IV ionizing and V preparing a composite flocculant. The invention also discloses the composite flocculant for treating papermaking wastewater, which is prepared according to the preparation method. The preparation method disclosed by the invention is simple and easy to implement, low in equipment dependence, easy to obtain raw materials, low in price and suitable for industrial production, and the prepared composite flocculant for treating papermaking wastewater has the advantages of low cost, good flocculation effect, excellent performance stability, small influence on environment, no secondary pollution and safety and environmental friendliness in use.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a composite flocculant for treating papermaking wastewater and a preparation method thereof.
Background
In recent years, with the rapid development of the papermaking industry, the pollution of papermaking wastewater brings fatal threats to people, and frosts the snow at the current situation of water resource shortage in China. The nation and the place successively establish and perfect the legislation and regulation on the waste water, the discharge standard of the waste water from paper making is more and more strict, in addition, people are deeply aware year by year on preventing and controlling environmental pollution and improving self health, the treatment of the waste water from paper making becomes a difficult problem which paper making enterprises have to face, and the waste water from paper making is one of the key factors restricting the development of paper making industry.
The conventional water treatment method comprises three-stage treatment such as physical and chemical treatment, biological treatment, advanced treatment and the like. The physicochemical treatment process, namely coagulation and sedimentation, is one of the most important treatment units in water and wastewater treatment. The flocculating agent is required to be added in the coagulation process to realize solid-liquid separation, and the quality of the flocculating agent directly influences the treatment effect of the coagulation precipitation process, so that the research and development of novel and efficient flocculating agents are always the pillar industry of important development in the field of water treatment and the basic industry of water industry and water pollution treatment engineering technology and equipment innovation development.
The existing flocculants used for wastewater treatment include two main types of inorganic flocculants and organic flocculants, such as polyaluminium chloride, polyferric chloride, polyacrylamide and the like, and cationic quaternary ammonium salt type polyacrylamide and other flocculants are developed in recent years. When the inorganic flocculant is singly adopted, the flocculation effect is good, but the dosage is large, the cost is high, and the removal effect on organic matters is not ideal. The organic flocculant has strong organic matter removing capacity, but has higher unit price, unobvious effect on other impurities such as phosphate radical, toxic hydrolysis and degradation products and high cost. The inorganic-organic composite flocculant overcomes the defects of small formed floc, low sedimentation speed, high dosage and the like of the inorganic flocculant, overcomes the defects of high manufacturing cost and the like of the organic flocculant, and becomes a development hotspot of the flocculant. However, in the prior art, due to uneven mixing and interaction among different types of flocculants, the flocculation effect of the composite flocculant is often reduced, so that the performance of the composite flocculant is unstable, and in addition, the preparation cost of the composite flocculant is higher.
Therefore, the composite flocculant for treating the papermaking wastewater, which is low in price, stable in performance, good in flocculation effect and small in dosage, is developed, meets the market demand, has wide market value and application prospect, and has a positive effect on promoting the development of the papermaking industry.
Disclosure of Invention
The invention mainly aims to provide a composite flocculant for treating papermaking wastewater and a preparation method thereof. The prepared composite flocculant for treating papermaking wastewater overcomes the technical problems that the composite flocculant in the prior art is high in preparation cost, poor in flocculation effect and unstable in performance due to uneven mixing and interaction of different types of flocculants, and has the advantages of low cost, good flocculation effect, excellent performance stability, small influence on environment, no secondary pollution, safety in use and environmental friendliness.
In order to achieve the above purpose, the invention provides a preparation method of a composite flocculant for treating papermaking wastewater, which comprises the following steps:
preparation of triazine polyamide polycondensates: dissolving tartronic acid, 2, 4-diamino-6-vinyl-S-triazine and polymerization inhibitor in high boiling point solvent, reacting at 85-95 deg.c under normal pressure for 1.5-2.5 hr, heating to 105-115 ℃ for reaction for 2-3 hours, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine and tetrabutylammonium bromide, heating to 200-220 ℃ for primary polycondensation for 4-6 hours, then transferring the reaction liquid into a reaction kettle, vacuumizing (500Pa), heating to 230-240 ℃, performing polycondensation reaction for 8-10 hours, cooling to room temperature, adjusting to normal pressure, precipitating in acetone, filtering, washing the product with dichloromethane for 4-6 times, and removing dichloromethane by rotary evaporation to obtain polymeric triazine polyamide polycondensate;
II preparation of triazine amido acrylonitrile copolymer: dissolving the polymeric triazine polyamide polycondensate prepared in the step I, 3-ethoxy-2- [ (2-furylmethyl) sulfonyl ] acrylonitrile, allyl 3-O-benzyl-alpha-L-rhamnopyranoside, N- (chloroacetyl) allylamine and an initiator in N-methylpyrrolidone, performing 600-900W microwave irradiation for 15-30 minutes at 80-90 ℃ in nitrogen or inert gas atmosphere, precipitating in ethanol, performing suction filtration, and drying in a vacuum drying oven at 70-80 ℃ for 10-15 hours to obtain the triazine polyamide-based acrylonitrile copolymer;
III modified active silicic acid: adding active silicic acid into trichloromethane, adding hyperbranched polyethyleneimine, stirring and reacting at 90-100 ℃ for 4-6 hours, and then performing rotary evaporation to remove trichloromethane to obtain modified active silicic acid;
IV, ionizing: dissolving the triazine acylamino acrylonitrile copolymer prepared in the step II and the modified active silicic acid prepared in the step III in N, N-dimethylformamide, stirring and reacting at 60-80 ℃ for 6-8 hours, precipitating in acetone, and performing rotary evaporation to remove acetone to obtain the ionic triazine acylamino acrylonitrile copolymer modified active silicic acid;
v, preparation of a composite flocculant: and (3) adding the ionic triazine polyamide-based acrylonitrile copolymer modified active silicic acid prepared in the step (IV) and polystyrene sulfonic acid into N-methyl pyrrolidone, stirring and reacting for 4-6 hours at the temperature of 60-80 ℃, and then removing the N-methyl pyrrolidone by rotary evaporation to obtain the composite flocculant for treating papermaking wastewater.
Furthermore, in the step I, the mass ratio of the hydroxymalonic acid to the 2, 4-diamino-6-vinyl-S-triazine to the polymerization inhibitor to the high boiling point solvent to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 4-dimethylaminopyridine to the tetrabutylammonium bromide is 1:1.14 (0.1-0.3) to (6-10) to 0.4:0.2: 0.1.
Preferably, the polymerization inhibitor is selected from one or more of methyl hydroquinone, tetrachlorobenzoquinone and l, 4-naphthoquinone.
Preferably, the high boiling point solvent is selected from one or more of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
Furthermore, the mass ratio of the polymeric triazine polyamide polycondensate, the 3-ethoxy-2- [ (2-furylmethyl) sulfonyl ] acrylonitrile, the allyl 3-O-benzyl-alpha-L-rhamnopyranoside, the N- (chloroacetyl) allylamine, the initiator and the N-methylpyrrolidone in the step II is 2:0.5:1:0.7 (0.01-0.03) to (8-12).
Preferably, the initiator is selected from one or more of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the inert gas is selected from one or more of helium, neon and argon.
Furthermore, the mass ratio of the active silicic acid, the trichloromethane and the hyperbranched polyethyleneimine in the step III is (2-3) to (5-10) to 0.6.
Furthermore, the mass ratio of the triazine polyamide-based acrylonitrile copolymer, the modified active silicic acid and the N, N-dimethylformamide in the step IV is 1:0.3 (5-10).
Furthermore, the mass ratio of the ionic triazine polyamide-based acrylonitrile copolymer modified active silicic acid, the polystyrene sulfonic acid and the N-methyl pyrrolidone in the step V is 1:0.4 (5-10).
A composite flocculant for treating papermaking wastewater is prepared by adopting the preparation method of the composite flocculant for treating papermaking wastewater.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the composite flocculant for treating papermaking wastewater disclosed by the invention is simple and easy to prepare, low in equipment dependence, easy to obtain raw materials, low in price and suitable for industrial production.
(2) The composite flocculant for treating papermaking wastewater disclosed by the invention overcomes the technical problems that the preparation cost of the composite flocculant in the prior art is high, and the flocculation effect is poor and the performance is unstable due to uneven mixing and interaction of different types of flocculants, and has the advantages of low cost, good flocculation effect, excellent performance stability, small influence on the environment, no secondary pollution, safety in use and environmental friendliness.
(3) The composite flocculant for treating papermaking wastewater disclosed by the invention introduces a polymerized triazine polyamide polycondensate, 3-ethoxy-2- [ (2-furylmethyl) sulfonyl ] acrylonitrile and an allyl 3-O-benzyl-alpha-L-rhamnopyranoside structure through copolymerization, so that the structure and the performance are more stable, the synergistic flocculation effect is better, and the bridging effect in water is better; through modifying active silicic acid, avoided its self to condense into the problem of gel, inorganic organic flocculation material is compound for the material has inorganic flocculant and organic flocculant's advantage concurrently, and the flocculation effect is more showing, flocculation efficiency is higher, through the modification, introduces ionic group, and rethread ion exchange passes through the ionic bond with polystyrene sulfonic acid in succession, makes the structure more stable, and the performance is homogeneous more stable, and can give the bacterinertness.
(4) The composite flocculant for treating papermaking wastewater disclosed by the invention has the synergistic effect of all components, and is beneficial to improving the comprehensive performance of the flocculant; pyran, glucoside, ethyoxyl, polyamide, acrylonitrile, polystyrene sulfonic acid and hyperbranched polyethyleneimine structures are introduced to synergistically improve the flocculation capacity, and benzene ring, acrylonitrile and triazine structures are introduced to improve the salt resistance and stain resistance.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
The raw materials used in the examples of the present invention were purchased from Mobei (Shanghai) Biotech limited.
Example 1
A preparation method of a composite flocculant for treating papermaking wastewater comprises the following steps:
preparation of triazine polyamide polycondensates: dissolving 10g of hydroxymalonic acid, 11.4g of 2, 4-diamino-6-vinyl-S-triazine and 1g of methylhydroquinone in 60g of dimethyl sulfoxide, reacting at 85 ℃ for 1.5 hours under normal pressure, heating to 105 ℃ for 2 hours, adding 4g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 2g of 4-dimethylaminopyridine and 1g of tetrabutylammonium bromide, heating to 200 ℃, carrying out primary polycondensation for 4 hours, transferring the reaction solution into a reaction kettle, vacuumizing (500Pa), heating to 230 ℃, carrying out polycondensation for 8 hours, cooling to room temperature, regulating to normal pressure, precipitating in acetone, carrying out suction filtration, washing a product for 4 times with dichloromethane, and carrying out rotary evaporation to remove dichloromethane to obtain a polymeric triazine polyamide polycondensate;
II preparation of triazine amido acrylonitrile copolymer: dissolving 20g of the polymeric triazine polyamide polycondensate prepared in the step I, 5g of 3-ethoxy-2- [ (2-furylmethyl) sulfonyl ] acrylonitrile, 10g of allyl 3-O-benzyl-alpha-L-rhamnopyranoside, 7g of N- (chloroacetyl) allylamine and 0.1g of azobisisobutyronitrile in 80g of N-methylpyrrolidone, irradiating the mixture for 15 minutes by using 600W microwaves at 80 ℃ in a nitrogen atmosphere, precipitating the mixture in ethanol, filtering the solution, and drying the filtered product in a vacuum drying oven at 70 ℃ for 10 hours to obtain the triazine polyamide acrylonitrile copolymer;
III modified active silicic acid: adding 20g of active silicic acid into 50g of trichloromethane, adding 6g of hyperbranched polyethyleneimine, stirring and reacting at 90 ℃ for 4 hours, and then performing rotary evaporation to remove trichloromethane to obtain modified active silicic acid;
IV, ionizing: dissolving 10g of the triazine acylamino acrylonitrile copolymer prepared in the step II and 3g of the modified active silicic acid prepared in the step III in 50g of N, N-dimethylformamide, stirring and reacting at 60 ℃ for 6 hours, precipitating in acetone, and performing rotary evaporation to remove the acetone to obtain the ionic triazine acylamino acrylonitrile copolymer modified active silicic acid;
v, preparation of a composite flocculant: and (3) adding 10g of ionic triazine polyamide-based acrylonitrile copolymer modified active silicic acid prepared in the step (IV) and 4g of polystyrene sulfonic acid into 50g of N-methyl pyrrolidone, stirring and reacting at 60 ℃ for 4 hours, and then carrying out rotary evaporation to remove the N-methyl pyrrolidone, thereby obtaining the composite flocculant for treating papermaking wastewater.
A composite flocculant for treating papermaking wastewater is prepared by adopting the preparation method of the composite flocculant for treating papermaking wastewater.
Example 2
A preparation method of a composite flocculant for treating papermaking wastewater comprises the following steps:
preparation of triazine polyamide polycondensates: dissolving 10g of hydroxymalonic acid, 11.4g of 2, 4-diamino-6-vinyl-S-triazine and 1.5g of tetrachlorobenzoquinone in 70g of N, N-dimethylformamide, reacting at 87 ℃ for 1.7 hours under normal pressure, heating to 108 ℃ for 2.3 hours, adding 4g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 2g of 4-dimethylaminopyridine and 1g of tetrabutylammonium bromide, heating to 205 ℃, carrying out primary polycondensation for 4.5 hours, transferring the reaction solution into a reaction kettle, vacuumizing (500Pa), heating to 232 ℃, carrying out polycondensation for 8.5 hours, cooling to room temperature, adjusting to normal pressure, precipitating in acetone, carrying out suction filtration, washing the product with dichloromethane for 5 times, and then evaporating to remove dichloromethane to obtain a polymeric triazine polyamide polycondensate;
II preparation of triazine amido acrylonitrile copolymer: dissolving 20g of the polymeric triazine polyamide polycondensate prepared in the step I, 5g of 3-ethoxy-2- [ (2-furylmethyl) sulfonyl ] acrylonitrile, 10g of allyl 3-O-benzyl-alpha-L-rhamnopyranoside, 7g of N- (chloroacetyl) allylamine and 0.15g of azobisisoheptonitrile in 90g of N-methylpyrrolidone, irradiating for 18 minutes by 650W microwave under the atmosphere of helium and 82 ℃, precipitating in ethanol, filtering, and drying in a vacuum drying oven at 72 ℃ for 11 hours to obtain the triazine polyamide-based acrylonitrile copolymer;
III modified active silicic acid: adding 23g of active silicic acid into 65g of trichloromethane, adding 6g of hyperbranched polyethyleneimine, stirring and reacting for 5 hours at 94 ℃, and then performing rotary evaporation to remove trichloromethane to obtain modified active silicic acid;
IV, ionizing: dissolving 10g of the triazine acylamino acrylonitrile copolymer prepared in the step II and 3g of the modified active silicic acid prepared in the step III in 65g of N, N-dimethylformamide, stirring and reacting at 66 ℃ for 6.6 hours, then precipitating in acetone, and removing the acetone by rotary evaporation to obtain the ionic triazine acylamino acrylonitrile copolymer modified active silicic acid;
v, preparation of a composite flocculant: and (3) adding 10g of ionic triazine polyamide-based acrylonitrile copolymer modified active silicic acid prepared in the step (IV) and 4g of polystyrene sulfonic acid into 66g of N-methyl pyrrolidone, stirring and reacting at 68 ℃ for 5 hours, and then carrying out rotary evaporation to remove the N-methyl pyrrolidone, thereby obtaining the composite flocculant for treating papermaking wastewater.
A composite flocculant for treating papermaking wastewater is prepared by adopting the preparation method of the composite flocculant for treating papermaking wastewater.
Example 3
A preparation method of a composite flocculant for treating papermaking wastewater comprises the following steps:
preparation of triazine polyamide polycondensates: dissolving 10g of hydroxymalonic acid and 11.4g of 2, 4-diamino-6-vinyl-S-triazine and 2g of l, 4-naphthoquinone in 76g of N-methylpyrrolidone, reacting at 89 ℃ for 2 hours under normal pressure, heating to 109 ℃ for 2.5 hours, adding 4g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 2g of 4-dimethylaminopyridine and 1g of tetrabutylammonium bromide, heating to 210 ℃, carrying out primary polycondensation for 5.2 hours, transferring the reaction solution into a reaction kettle, vacuumizing (500Pa), heating to 236 ℃, carrying out polycondensation for 9.2 hours, cooling to room temperature, adjusting to normal pressure, precipitating in acetone, carrying out suction filtration, washing the product with dichloromethane for 6 times, and evaporating to remove dichloromethane to obtain a polymeric triazine polyamide polycondensate;
II preparation of triazine amido acrylonitrile copolymer: dissolving 20g of the polymeric triazine polyamide polycondensate prepared in the step I, 5g of 3-ethoxy-2- [ (2-furylmethyl) sulfonyl ] acrylonitrile, 10g of allyl 3-O-benzyl-alpha-L-rhamnopyranoside, 7g of N- (chloroacetyl) allylamine and 0.2g of azobisisobutyronitrile in 99g of N-methylpyrrolidone, irradiating the mixture for 22 minutes by using 750W microwaves at 87 ℃ in a neon atmosphere, precipitating the mixture in ethanol, filtering the mixture, and drying the mixture for 13 hours in a vacuum drying oven at 76 ℃ to obtain the triazine polyamide-based acrylonitrile copolymer;
III modified active silicic acid: adding 26g of active silicic acid into 85g of trichloromethane, adding 6g of hyperbranched polyethyleneimine, stirring and reacting at 97 ℃ for 5.3 hours, and performing rotary evaporation to remove trichloromethane to obtain modified active silicic acid;
IV, ionizing: dissolving 10g of the triazine acylamino acrylonitrile copolymer prepared in the step II and 3g of the modified active silicic acid prepared in the step III in 86g of N, N-dimethylformamide, stirring and reacting at 73 ℃ for 7.2 hours, then precipitating in acetone, and removing the acetone by rotary evaporation to obtain the ionic triazine acylamino acrylonitrile copolymer modified active silicic acid;
v, preparation of a composite flocculant: and (3) adding 10g of ionic triazine polyamide-based acrylonitrile copolymer modified active silicic acid prepared in the step (IV) and 4g of polystyrene sulfonic acid into 85g of N-methyl pyrrolidone, stirring and reacting at 73 ℃ for 4-6 hours, and then carrying out rotary evaporation to remove the N-methyl pyrrolidone, thereby obtaining the composite flocculant for treating papermaking wastewater.
A composite flocculant for treating papermaking wastewater is prepared by adopting the preparation method of the composite flocculant for treating papermaking wastewater.
Example 4
A preparation method of a composite flocculant for treating papermaking wastewater comprises the following steps:
preparation of triazine polyamide polycondensates: dissolving 10g of hydroxymalonic acid, 11.4g of 2, 4-diamino-6-vinyl-S-triazine and 2.5g of polymerization inhibitor in 95g of high-boiling-point solvent, reacting at 94 ℃ for 2.4 hours under normal pressure, heating to 113 ℃ for reaction for 2.8 hours, adding 4g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 2g of 4-dimethylaminopyridine and 1g of tetrabutylammonium bromide, heating to 215 ℃, carrying out primary polycondensation for 5.5 hours, transferring the reaction solution into a reaction kettle, vacuumizing (500Pa), heating to 238 ℃, carrying out polycondensation for 9.7 hours, cooling to room temperature, adjusting to normal pressure, precipitating in acetone, carrying out suction filtration, washing the product with dichloromethane for 5 times, and carrying out rotary evaporation to remove dichloromethane to obtain a polymeric triazine polyamide polycondensate; the polymerization inhibitor is a mixture formed by mixing methyl hydroquinone, chloranil and l, 4-naphthoquinone according to the mass ratio of 1:3: 2; the high-boiling-point solvent is a mixture formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to a mass ratio of 3:4: 2;
II preparation of triazine amido acrylonitrile copolymer: dissolving 20g of the polymeric triazine polyamide polycondensate prepared in the step I, 5g of 3-ethoxy-2- [ (2-furylmethyl) sulfonyl ] acrylonitrile, 10g of allyl 3-O-benzyl-alpha-L-rhamnopyranoside, 7g of N- (chloroacetyl) allylamine and 0.25g of initiator in 115g of N-methylpyrrolidone, performing 850W microwave irradiation for 27 minutes at 88 ℃ in argon atmosphere, precipitating in ethanol, performing suction filtration, and drying in a vacuum drying oven at 78 ℃ for 14 hours to obtain the triazine polyamide acrylic nitrile copolymer; the initiator is a mixture formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5;
III modified active silicic acid: adding 28g of active silicic acid into 95g of trichloromethane, adding 6g of hyperbranched polyethyleneimine, stirring and reacting at 98 ℃ for 5.5 hours, and then performing rotary evaporation to remove trichloromethane to obtain modified active silicic acid;
IV, ionizing: dissolving 10g of the triazine acylamino acrylonitrile copolymer prepared in the step II and 3g of the modified active silicic acid prepared in the step III in 95g of N, N-dimethylformamide, stirring and reacting at 78 ℃ for 7.8 hours, then precipitating in acetone, and removing the acetone by rotary evaporation to obtain the ionic triazine acylamino acrylonitrile copolymer modified active silicic acid;
v, preparation of a composite flocculant: and (3) adding 10g of ionic triazine polyamide-based acrylonitrile copolymer modified active silicic acid prepared in the step (IV) and 4g of polystyrene sulfonic acid into 95g of N-methyl pyrrolidone, stirring and reacting at 78 ℃ for 5.8 hours, and then carrying out rotary evaporation to remove the N-methyl pyrrolidone, thereby obtaining the composite flocculant for treating papermaking wastewater.
A composite flocculant for treating papermaking wastewater is prepared by adopting the preparation method of the composite flocculant for treating papermaking wastewater.
Example 5
A preparation method of a composite flocculant for treating papermaking wastewater comprises the following steps:
preparation of triazine polyamide polycondensates: dissolving 10g of hydroxymalonic acid, 11.4g of 2, 4-diamino-6-vinyl-S-triazine and 3g of methylhydroquinone in 100g of N, N-dimethylformamide, reacting at 95 ℃ for 2.5 hours under normal pressure, heating to 115 ℃ for 3 hours, adding 4g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 2g of 4-dimethylaminopyridine and 1g of tetrabutylammonium bromide, heating to 220 ℃, carrying out primary polycondensation for 6 hours, transferring the reaction solution into a reaction kettle, vacuumizing (500Pa), heating to 240 ℃, carrying out secondary polycondensation for 10 hours, cooling to room temperature, regulating to normal pressure, precipitating in acetone, carrying out suction filtration, washing a product for 6 times with dichloromethane, and carrying out rotary evaporation to remove dichloromethane to obtain a polymeric triazine polyamide polycondensate;
II preparation of triazine amido acrylonitrile copolymer: dissolving 20g of the polymeric triazine polyamide polycondensate prepared in the step I, 5g of 3-ethoxy-2- [ (2-furylmethyl) sulfonyl ] acrylonitrile, 10g of allyl 3-O-benzyl-alpha-L-rhamnopyranoside, 7g of N- (chloroacetyl) allylamine and 0.3g of azobisisoheptonitrile in 120g of N-methylpyrrolidone, performing 900W microwave irradiation for 30 minutes at 90 ℃ in a nitrogen atmosphere, precipitating in ethanol, performing suction filtration, and drying for 15 hours at 80 ℃ in a vacuum drying oven to obtain the triazine polyamide acrylonitrile copolymer;
III modified active silicic acid: adding 30g of active silicic acid into 100g of trichloromethane, adding 6g of hyperbranched polyethyleneimine, stirring and reacting at 100 ℃ for 6 hours, and then performing rotary evaporation to remove trichloromethane to obtain modified active silicic acid;
IV, ionizing: dissolving 10g of the triazine acylamino acrylonitrile copolymer prepared in the step II and 3g of the modified active silicic acid prepared in the step III in 100g of N, N-dimethylformamide, stirring and reacting at 80 ℃ for 8 hours, precipitating in acetone, and performing rotary evaporation to remove the acetone to obtain the ionic triazine acylamino acrylonitrile copolymer modified active silicic acid;
v, preparation of a composite flocculant: and (3) adding 10g of ionic triazine polyamide-based acrylonitrile copolymer modified active silicic acid prepared in the step (IV) and 4g of polystyrene sulfonic acid into 100g of N-methyl pyrrolidone, stirring and reacting at 80 ℃ for 6 hours, and then carrying out rotary evaporation to remove the N-methyl pyrrolidone, thereby obtaining the composite flocculant for treating papermaking wastewater.
A composite flocculant for treating papermaking wastewater is prepared by adopting the preparation method of the composite flocculant for treating papermaking wastewater.
Comparative example
Commercially available polyacrylamide flocculants.
The composite flocculant for treating papermaking wastewater prepared in the above examples 1 to 5 and the comparative flocculant were subjected to flocculation performance tests, the test methods were as follows: taking kaolin suspension with the mass fraction of 1% and the turbidity of A, respectively measuring the turbidity of the suspension when 60ppm, 30ppm and 10ppm of flocculating agents are respectively added, and testing the turbidity B. Turbidity removal rate (a-B)/B × 100%. The test results are shown in Table 1.
As can be seen from table 1, the composite flocculant for treating papermaking wastewater disclosed in the embodiment of the present invention has a more excellent flocculation effect than the polyacrylamide flocculant in the prior art.
TABLE 1
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A preparation method of a composite flocculant for treating papermaking wastewater is characterized by comprising the following steps:
preparation of triazine polyamide polycondensates: dissolving tartronic acid, 2, 4-diamino-6-vinyl-S-triazine and polymerization inhibitor in high boiling point solvent, reacting at 85-95 deg.c under normal pressure for 1.5-2.5 hr, heating to 105-115 ℃ for reaction for 2-3 hours, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 4-dimethylaminopyridine and tetrabutylammonium bromide, heating to 200-220 ℃ for primary polycondensation for 4-6 hours, then transferring the reaction liquid into a reaction kettle, vacuumizing to 500Pa, heating to 230-240 ℃, performing polycondensation reaction for 8-10 hours, cooling to room temperature, adjusting to normal pressure, precipitating in acetone, filtering, washing the product with dichloromethane for 4-6 times, and removing dichloromethane by rotary evaporation to obtain polymeric triazine polyamide polycondensate; the mass ratio of the hydroxymalonic acid to the 2, 4-diamino-6-vinyl-S-triazine to the polymerization inhibitor to the high-boiling-point solvent to the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 4-dimethylaminopyridine to the tetrabutylammonium bromide is 1:1.14 (0.1-0.3) to (6-10) to 0.4:0.2: 0.1;
II preparation of triazine amido acrylonitrile copolymer: dissolving the polymeric triazine polyamide polycondensate prepared in the step I, 3-ethoxy-2- [ (2-furylmethyl) sulfonyl ] acrylonitrile, allyl 3-O-benzyl-alpha-L-rhamnopyranoside, N- (chloroacetyl) allylamine and an initiator in N-methylpyrrolidone, performing microwave irradiation at 600-900W for 15-30 minutes at 80-90 ℃ in an inert gas atmosphere, precipitating in ethanol, performing suction filtration, and drying in a vacuum drying oven at 70-80 ℃ for 10-15 hours to obtain the triazine polyamide acrylic nitrile copolymer; the mass ratio of the polymeric triazine polyamide polycondensate to the 3-ethoxy-2- [ (2-furylmethyl) sulfonyl ] acrylonitrile to the allyl 3-O-benzyl-alpha-L-rhamnopyranoside to the N- (chloroacetyl) allylamine to the initiator to the N-methylpyrrolidone is 2:0.5:1:0.7 (0.01-0.03) to (8-12);
III modified active silicic acid: adding active silicic acid into trichloromethane, adding hyperbranched polyethyleneimine, stirring and reacting at 90-100 ℃ for 4-6 hours, and then performing rotary evaporation to remove trichloromethane to obtain modified active silicic acid; the mass ratio of the active silicic acid to the trichloromethane to the hyperbranched polyethyleneimine is (2-3) to (5-10) to 0.6;
IV, ionizing: dissolving the triazine acylamino acrylonitrile copolymer prepared in the step II and the modified active silicic acid prepared in the step III in N, N-dimethylformamide, stirring and reacting at 60-80 ℃ for 6-8 hours, precipitating in acetone, and performing rotary evaporation to remove acetone to obtain the ionic triazine acylamino acrylonitrile copolymer modified active silicic acid; the mass ratio of the triazine polyamide-based acrylonitrile copolymer to the modified active silicic acid to the N, N-dimethylformamide is 1:0.3 (5-10);
v, preparation of a composite flocculant: adding the ionic triazine polyamide-based acrylonitrile copolymer modified active silicic acid prepared in the step IV and polystyrene sulfonic acid into N-methyl pyrrolidone, stirring and reacting for 4-6 hours at 60-80 ℃, and then removing the N-methyl pyrrolidone by rotary evaporation to obtain the composite flocculant for treating papermaking wastewater; the mass ratio of the ionic triazine amido acrylonitrile copolymer modified active silicic acid to the polystyrene sulfonic acid to the N-methyl pyrrolidone is 1:0.4 (5-10).
2. The method for preparing the composite flocculant for treating papermaking wastewater according to claim 1, wherein the polymerization inhibitor is one or more selected from methyl hydroquinone, tetrachlorobenzoquinone and l, 4-naphthoquinone.
3. The preparation method of the composite flocculant for treating papermaking wastewater according to claim 1, wherein the high-boiling-point solvent is one or more selected from dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone.
4. The preparation method of the composite flocculant for treating papermaking wastewater according to claim 1, characterized in that the initiator is one or more selected from azobisisobutyronitrile and azobisisoheptonitrile; the inert gas is selected from one or more of nitrogen, helium, neon and argon.
5. The composite flocculant for treating papermaking wastewater, which is prepared by the preparation method of the composite flocculant for treating papermaking wastewater according to any one of claims 1 to 4.
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